Metal-mediated couplings of a diphosphastibolyl ring anion, [1,4,2-P2SbC2But2]-: Synthesis and characterisation of novel antimony-containing cage compounds

Steven J. Black, David E. Hibbs, Michael B. Hursthouse, Cameron Jones, K. M.Abdul Malik, Ryan C. Thomas

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Two equivalents of the diphosphastibolyl ring anion, [1,4,2-P2SbC2But2]- reacted with FeCl3 to produce an antimony-containing cage compound, P4Sb2C4But4, via an oxidative coupling mechanism. This cage underwent an intramolecular rearrangement reaction when treated with [W(CO)5(thf)] (thf = tetrahydrofuran) to produce the complex [{W(CO)5}P4Sb2C4But 4], which X-ray crystallography shows to contain a three-membered PPC 'diphosphirane' ring. Treatment of cis-[PtCl2(PEt3)2] with 1 equivalent of [1,4,2-P2SbC2But2]- yielded the first example of a complex, trans-[PtCl(PEt3)21-P2SbC 2But2], containing a solely η1-co-ordinated diphosphastibolyl ring. The crystal structure of this compound shows the heterocyclic ring to retain its aromaticity after co-ordination. Treatment of cis-[PtCl2(PEt3)2] with 2 equivalents of [1,4,2-P2SbC2But2]- initiated a ring-coupling reaction at the metal to give the novel cage complex cis-[Pt(PEt3)22-P4Sb 2C4But4]. The molecular structure of the cage shows it to contain a highly strained, dianionic ligand, [P4Sb2C4But4] 2-, which chelates the platinum through antimony and phosphorus atoms. Unusual features in the 31P-{1H} NMR spectrum of the complex are described.

Original languageEnglish
Pages (from-to)4321-4326
Number of pages6
Issue number22
Publication statusPublished - 21 Nov 1997
Externally publishedYes

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